VICE - A Comprehensive

Guide to Cooking Meth on

‘Breaking Bad’
Disclaimer: Cooking and/or selling methamphetamine
and other controlled substances is illegal unless you are
working under the aegis of a pharmaceutical company.

As a chemist and someone interested in psychoactive

drugs, I'm frequently asked if I watch the AMC series
Breaking Bad and if the show accurately portrays
clandestine chemistry. I am a huge fan of the show and
frequently watch it while working in the lab late at night.
Although the clandestine chemistry always appeared
accurate at first glance, I desired a more detailed critique
of Walter White's syntheses. But season after season my
thirst for technical analysis was left unquenched; I found
a few articles that touched on the clandestine chemistry,
but none were comprehensive. After dedicating the last
seven years of my life to organic chemistry, it felt like a
natural departure from writing my dissertation to examine
this matter more closely.

Nagai Nagayoshi(1844-1929)

N-methyl-1-phenylpropan-2-amine or methamphetamine
was first synthesized from the naturally occurring alkaloid
ephedrine by Japanese chemist Nagai Nagayoshi in 1893
while researching the structure of ephedrine [1]. Meth's
psychostimulant effect does not seem to have been
noticed until the mid-30s when Friedrich Hauschild
discovered it at the Berlin based pharmaceutical
company Temmler. By the 1950s stimulants became a
regular part of the American routine, and a flourishing
black-market in diverted pharmaceuticals soon
developed. This supply began to wither in the 1960s as
law enforcement prosecuted over-prescribing doctors
and placed pressure on pharmaceutical companies to
withdraw certain products. Many believe the first
clandestine labs originated in the California bay area from
this environment around 1962 [2].

When it comes to making meth, the difference between

cooking and synthesis should be acknowledged. In the
same manner anyone can learn how to cook a fancy
meal, anyone can be taught to cook meth regardless of
chemistry education—cooking meth may be just a little
more explosive. In fact, cooking meth can be extremely
dangerous because a lack of chemical knowledge puts
the cook (and anyone else nearby) at serious risk of
injury. As Gus's assistant Victor in "Box Cutter" (S.4E.1)
states, "It's called a cook, because everything comes
down to following a recipe." Walt appropriately asks him,
"What happens when you get a bad barrel of precursor?
How would you even know?" and "What happens in the
summer when the humidity level rises and your product
goes cloudy?" These are important points that someone
just following a recipe may not be able to deal with. A
skilled chemist like Walt understands the chemistry
allowing him to alter or adapt the synthesis as necessary.

In early episodes, Walt and Jessie produce

methamphetamine using the Nagai method—the same
synthetic route used by Nagai Nagayoshi in the first
recorded methamphetamine synthesis. The Nagai
method employs pseudoephedrine as a precursor, which
is reduced with hydroiodic acid (HI) to yield
methamphetamine. This method was once the favorite of
small scale meth operations in America—along with the
misnamed "Nazi method," which was most common in
agricultural areas with access to liquid ammonia fertilizer
(Li/NH3 reduction or Birch reduction). Today small-scale
operators prefer the one pot "shake and bake" method, a
modified form of the Birch reduction [3].

Pseudoephedrine.

The Nagai method is portrayed twice in the pilot episode

(S.1E.1): first when Walt's DEA agent brother in law, Hank
Schrader, and his DEA pals raid Jessie's lab while Walt
rides along, and then again during the Winnebago cook
scene. The paraphernalia characteristic of this method is
seen as the agents storm through the house: coffee
filters, match books, road flares, iodine tinctures, boxes
and blister packs of OTC cold medicine, and mason jars
of transparent red and yellow solvents (from removing
the red wax coating and extracting pseudoephedrine
from cold medicine respectively).

As may now be obvious, the popularity of the Nagai

method stems from the ease of obtaining the necessary
chemicals. Pseudoephedrine is extracted (via water or
alcohol and coffee filters) from OTC cold medicine. Red
phosphorus needed to reduce elemental iodine (I2) to HI
and to recycle reformed I2 [4], is collected from
matchbook striker pads or road flares. (Walt and Jessie
use both as phosphorus sources at different times.) I2
crystals can be extracted from readily accessible
disinfectants. Once readied, pseudoephedrine, I2, and
red phosphorus are placed in a boiling flask along with
water and heated for varying lengths of time. The
resulting deep purple solution, a result of I2, is a telltale
sign of this reaction. (As acknowledged several times on
the show, care should be taken—unless intentionally
trying to kill a rival drug dealer who's holding a gun to
your head—to vent the toxic phosphine gas produced on
heating.) Once complete the reaction is worked up.

How to prepare l2 from Iodine tinctures.

In the pilot episode, Walt does this by making the solution

basic and then extracting it with an organic solvent. His
use of a plastic syringe to remove the organic solvent
layer is typical of clandestine cooks—an easier alternative
favored by legitimate chemists is a separatory funnel. By
bubbling the HCI gas into the solution, the resulting d-
methamphetamine is then precipitated as the HCl salt.

In the Nagai method, the β-hydroxyl group on ephedrine

or pseudoephedrine is protonated forming a hydronium
ion leaving group. A nucleophilic substitution reaction
then occurs with an iodide anion. Water is lost to give
iodoephedrine, which then undergoes reductive
dehalogenation by liberated H2 producing
methamphetamine [4]. The mechanism of the "emede
method," a previously popular clandestine procedure, is
equivalent; however, in this case it is performed in two
separate reactions, isolating the ephedrine halide, usually
Bromo- or Chloro-ephedrine, and then reducing it to
methamphetamine.

By the seventh episode of Season 1 ("A No Rough-Stuff-

Type Deal"), obtaining pseudoephedrine for the large-
scale production that Walt desires becomes an issue. To
circumvent this, Walt decides on an alternate synthesis—
reductive amination using P2P (phenylacetone) and
methylamine. Upon hearing he no longer has to smurf
pseudoephedrine, an infamously tedious process, Jessie
enthusiastically exclaims, "Yeah, science!" The synthesis
of methamphetamine using reductive amination is not
new; Japanese chemist Akira Ogata first used it in 1919
[5] with various modifications appearing in the scientific
and patent literature ever since. Obtaining methylamine
required for this reaction—which is on the DEA watch list,
a list of chemicals the DEA has classified as having use in
drug manufacture—becomes a major plot line throughout
the seasons.

Methylamine.

In reductive amination, a ketone or aldehyde is

condensed with an amine to form an imine or Schiff base
intermediate, which is then reduced to an amine. In this
case, P2P and methylamine are condensed forming the
imine; this is then reduced by adding hydrogen to
methamphetamine. The steps can be performed in
separate reactions or together (one-pot). In Secrets of
Methamphetamine Manufacture 7th edition, author and
former meth cook Uncle Fester discusses several
possible reduction methods for reductive amination—
including NaCNBH4, mercury aluminum amalgam
reductions, and Hydrogen bomb using H2/PtO2 or Raney
nickel [6]. Based on several scenes referencing or
depicting aluminum metal and mention of "mercury
amalgam," Walt and Jesse use the former where
aluminum foil is "activated" with HgCl2 to give aluminum
amalgam. As Uncle Fester outlines, Walt and Jessie use a
one-pot reaction where P2P, 40 percent aqueous
methylamine, and alcohol are mixed with mercury
amalgam—mercury amalgam reductions have a
characteristic foaming cloudy grey appearance, as
portrayed in the cook scene from "Hazard Pay" (S.5E.3).
Reaction of P2P and methylamine produces an imine
which can then be reduced to racemic d-, l-
methamphetamine.

Although H2 is generated, the reduction actually involves

an internal electrolytic process involving electron transfer
from the metal that forms a radical carbon and
subsequent hydrogen abstractions from solvent. Once
complete, the reaction is worked up and product-
obtained by vacuum distillation. This is Walt's preferred
reduction. In "Green Light" (S.3E.4) Walt criticizes
Jessie's product, derogatorily stating he probably used a
platinum dioxide reduction. However, Jessie states he
used "mercury aluminum amalgam" because "dioxide's
too hard to keep wet," which surprises Walt.

This statement likely refers to the fact that PtO2, or

Adam's catalyst, is pyrophoric, meaning it ignites if
exposed to open air. (A clandestine meth chemist using
the pseudonym Loius Feech writes of his own experience
with PtO2 spontaneously exploding in his lab [7] in his
guide Large Scale Methamphetamine Manufacture.) PtO2
is a perfectly good reducing agent and was at one point
common in clandestine methamphetamine labs [8].
However it's pyrophoric nature and cost are downfalls.
There is some suggestion Walt may have even used PtO2
at one point—perhaps in the first P2P cook in "A No
Rough-Stuff-Type Deal" (S.1E.7). One of the listed items
Jessie gets for Walt is hydrogen gas. (This wouldn't be
used with a mercury amalgam reduction but would be
useful for a heterogeneous reduction employing a
reducing agent such as PtO2.)

In 1980 the DEA placed P2P into Schedule II of the

Controlled Substances Act, making it illegal to buy, sell,
or possess without a controlled substance license. This is
one of the earliest examples of the odd and unfortunate
habit of making pharmacologically inert chemicals illegal
because career criminals "could" misuse them. Although
P2P became harder to purchase, this did little to impact
methamphetamine's availability, because clandestine
chemists began synthesizing P2P themselves. Meanwhile
clandestine operations became more complex,
dangerous, and environmentally hazardous. The
resourceful clandestine chemists adopted several well-
known methods to synthesize P2P [9]. (Details of these
are available in the latest edition of Uncle Fester's Secrets
of Methamphetamine Manufacture or his Advanced
Techniques of Clandestine Psychedelic and
Amphetamine Manufacture.) The clandestine favorite for
P2P synthesis has always been phenylacetic acid (PAA),
which is also that used by Walt and Jessie [8, 9]. PAA is
mentioned in "Sunset" (S 3.E.6) when Gale asks Walt
about tapering its addition rate and in "Salud" (S4.E10)
when Jessie criticizes the cartel, whom he's visiting in
Mexico for not having PAA ready.

There are a number of ways to make P2P from PAA. The

list Walt gives Jessie in "A No Rough-Stuff-Type Deal"
(S.1E.7) contains two items: thorium nitrate and a tube
furnace indicative of a dehydrocarboxylation reaction.
Thorium nitrate is used to generate thorium dioxide
(ThO2), a radioactive metal oxide catalyst used in the
relatively complex—though high yielding—gas phase
reaction in a heated tube furnace. Mention of "thorium
oxide," a moniker of ThO2 and a "catalyst bed" in "Más"
(S3.E.5), further supports this. In dehydrocarboxylation,
two carboxylic acids are vaporized—in this case PAA and
acetic acid—and passed through a catalyst bed enclosed
by a heated tube furnace. These form the desired
asymmetric ketone (P2P), some undesirable symmetric
ketones, acetone, dibenzylketone, and the side products
CO2 and water. The resulting crude brownish oil is
collected. After separation from the aqueous water layer,
the P2P is purified via vacuum distillation.

Dehydrocarboxylation of phenylacetic acid and acetic

acid to produce P2P

From the 1960s to the mid-1980s, reductive amination

was the method of choice for clandestine
methamphetamine production. Enterprising biker gangs
who dominated the trade at this time mostly ran these
operations. (The slang term "crank" for
methamphetamine allegedly originated from Biker's
transporting meth in the crankshafts of their bikes.)
Reductive amination is less common today. Reference to
this occurs in "Seven Thirty-Seven" (S.2E.2) when Hank
shows his surprise after being shown the video of the
methylamine heist. He says, "P2P––they're cooking old
school biker meth." Increased DEA restrictions, including
placement of PAA on its "watch list," led to a switch to
ephedrine based syntheses. While ephedrine was the
initial choice, additional controls led to greater use of
pseudoephedrine. While pseudoephedrine remains
available over-the-counter today, the 2005 Combat
Methamphetamine Epidemic Act (CMEA) title VII limits
retail purchases and keeps records on all sales. Aside
from limited short-term impacts, these legislative efforts
failed to reduce availability of methamphetamine—the
DEA Domestic Drug Seizure Statistics indicate meth
availability may have even increased in recent years with
3,898 kgs confiscated in 2012 from 2,481 in 2011. While
domestic large-scale clandestine labs have been
impacted, small-scale (less than two ounces) labs have
become increasingly common, representing 81 percent of
seized domestic laboratories in 2006 [3]. These small-
scale domestic labs only provide a minor portion of the
current US meth supply—the majority originating in
Mexican cartel operated super-labs [2,3]. Showing the
scale of these operations, one 2012 bust of a Guadalajara
based super-lab allegedly confiscated 15 tons of high
purity methamphetamine [10]. The Mexican
government's new controls have affected ephedrine and
pseudoephedrine availability, leading to a significant
portion of Mexican super labs switching back to reductive
amination, specifically P2P prepared from PAA [11,12].
Phenylacetic acid.

Assuming all else is equal, most clandestine chemists

would choose a pseudoephedrine/ephedrine reduction
over reductive amination, because reduction of
pseudoephedrine produces the more potent d-
methamphetamine where reductive amination produces
much less potent racemic methamphetamine.

Non-superimposable mirror image forms of

methamphetamine. d- or (S-)-methamphetamine posses'
psychostimulant effects whereas -l or (R-)-
methamphetamine is a decongestant.

The potency difference is due to a chemical phenomenon

called chirality, not purity. Using the analogy of
handedness, Walt correctly explains chirality to his class
in "The Cat's in the Bag" (S.1E.2): "Just as your left hand
and your right hand are mirror images of one another...
identical and yet opposite, well so two organic
compounds can exist as mirror image forms of one
another." Since methamphetamine has one chiral center,
it can exist as two different mirror forms called
enantiomers (R- and S-based on an assigned priority of
substituent and d- and l- or + and - based on interaction
with plane polarized light). Since pseudoephedrine and
ephedrine are themselves chiral—containing the (S-)
configuration at the α-carbon—reduction produces
exclusively d-methamphetamine. On the other, reductive
amination produces a racemic or 50:50 mixture of d- and
l-methamphetamine. This is because the planar P2P-
methylamine imine is not chiral and hydrogen addition
occurs equally from either side of the planar imine bond.
Enantiomers often have distinct biological effects. Walt
explains, "Although they may look the same, they don't
always behave the same." He then illustrates this with the
textbook example of thalidomide, the morning sickness
pill that caused major birth defects, when sold as the
racemic mixture, due to the activity of the less active
enantiomer. Despite being a common pedagogical
illustration, the enantiomers of thalidomide interconvert in
the body because of the acidic hydrogen at the chiral
center. This means Walt's statement regarding R-
thalidomide being safe to give to a pregnant women is
technically false as the R-thalidomide would convert to
the teratogenic S-thalidomide in the body. Walt could
have better illustrated this phenomenon with
methamphetamine, since d-methamphetamine induces
classic stimulant effects, whereas l-methamphetamine is
only a weak stimulant but an excellent decongestant,
which is sold over-the-counter in Vicks® inhalers under
the pseudonym les-desoxyephedrine. The enantiomers
do not easily interconvert, because the chiral center of
methamphetamine does not have acidic hydrogen.

Despite using reductive amination, Walt implies his

product is enantiomerically pure in "Box cutter" (S.4E.1).
He asks Victor, "If our reduction is not stereospecific,
then how can our product be enantiomerically pure?"
Since he's not a chemist, Victor was unable to answer,
and anyways, before he could try, Gus slits his throat with
a box cutter. Unfortunately, we don't know if Walt is just
bluffing to try and save his and Jessie's life. If Walt's
product is pure d-methamphetamine, we can assume he
must use some technique to separate or "resolve" the
isomers, because the starting material is not chiral and
the reduction not stereospecific. Crystallography,
derivatization with a chiral group followed by physical
separation, and chiral chromatography are three
possibilities. Crystallography is relatively easy and high
yielding, and the resolving agent can be recycled, making
it a green option. We also know that Walt has professional
experience in crystallography, further pointing to this
method. In a crystallographic resolution, a diasteromeric
crystal or complex is formed between a chiral acid (like
D-tartaric acid) and the compound so they can be
separated. Unlike enantiomers, diastereomers have
distinct physical properties that allow cooks to separate
them using physical means like solubility. One chiral acid
used to resolve methamphetamine is Di-p-toluoyl-tartaric
acid [13]. One last point of pertinence—stereoselective
reductive aminations has been performed to synthesize
enatiomerically pure amphetamines, which containing a
primary amine, using asymmetric synthesis with chiral
auxiliary (R-) or (S-)-α-methylbenzylamine [14].

THE BLUE STUFF

Photo of blue meth from Kansas City Police Department
chief's blog.

Walt's methamphetamine becomes blue when he

switches from pseudoephedrine reduction to reductive
amination. When delivering this new product to cartel
drug dealer Tuco, in "Seven Thirty-Seven" (S.2E.1), Walt
says, "I used a different chemical process but it is every
bit as pure." In his own vernacular, Jessie also attests to
the quality saying, "It may be blue but it's the bomb."
After a short snort, Tuco agrees. "Tight, tight, tight, tight,
yeah, blue, yellow, pink, whatever man just keep bringing
me that," he yells.

As the pure HCl salt, methamphetamine is a colorless-

white crystalline solid. Illicit methamphetamine exists in a
number of colors, although colorless, white, and yellow
are most common. In the early days of clandestine
production, a brown waxy product called peanut butter
crank was common. Like Walt's blue, the colors result
from impurities formed during the reaction.

While I don't know why the writers chose blue, there may
be some logic. In the fifth chapter of Uncle Fester's
Secrets of Methamphetamine Manufacture 7th Edition
(2005), Uncle Fester describes an internet conversation
he had with "another cooker." During the pressure
gassing of a solution of 100 grams of methamphetamine
freebase in 1000 milliliters of Et2O, the "process
generates blue-colored product." During any chemical
reaction, "side reactions" occur which produce
impurities. Identity and quantity of impurities vary by
synthesis. Profiling the impurities, an analytical chemist
can often determine the method used to produce a
sample. However, the analytical chemist should take care
—P2P is actually produced as a side product in the Nagai
reduction of pseudoephedrine [15]. Crystallization,
chromatography, and other purification methods can
remove some impurities, but it is impossible to remove all,
and even a minor amount (less than one percent) can
influence a sample's color.

Despite its light blue coloration, Walt's product is highly

pure. "Box-cutter" (S.4E.1) opens with flashback to Gale
giddily setting up equipment in the laundromat super-lab.
He tells Gus that he has the sample he asked him to
analyze saying it is "quite good." He then lets us know it
was Walt's product: "I can not as of yet account for the
blue color." Gale goes on to guarantee Gus a purity of 96
percent for his own product. Walt's sample was 99
percent pure and "maybe even a touch beyond that."
Gale says to know for sure, he would "need an instrument
called a gas chromatograph." (A gas chromatograph or
gc vaporizes and separates the components of a sample
allowing impurities to be detected and quantified.)

Although at least one forensic report of blue

methamphetamine, an unimpressive powdered sample
adulterated with "blue chalk," predates Breaking Bad [16],
the show has certainly influenced the international
methamphetamine trade. A quick search of posts from
the last few years of various online drug discussion
forums shows that there has been many encounters of
high quality crystalline blue meth. In 2010, Kansas City
MO police chief Darryl Forté posted an entry on his blog,
saying blue meth was encountered several times in the
previous two months.

Surprisingly many of the law enforcement personal and

reporters in Kansas City failed to make the connection to
Breaking Bad. Two news reports speculated the blue
color might have been an ineffective attempt to fool the
chemical reagent field tests, which give a blue color when
tested positive for methamphetamine. It seems very
unlikely that highly successful criminals would think dying
their product blue would be sufficient to fool police
detection efforts. Another explanation was the blue color
was a marketing technique—drug dealers do use a
variety of methods to brand their products and colored
drugs are not new. Saint Patrick's day in Marietta, Ohio
apparently includes green crack cocaine [17]. Similarly
pink strawberry flavored cocaine has been encountered
by the DEA [18], and methamphetamine has been
available in a rainbow of colors and flavors [16].

The best source of information on the phenomenon is a

2010 "el Paso" intelligence bulletin which describes a
potential influence of Breaking Bad on the appearance of
blue methamphetamine in several states including Texas,
California, and Washington beginning in December 2009.
This "blue meth" or "blue ice" was allegedly more potent
and expensive—with two samples found to be an
impressive 98.4 and 98.2 percent pure d-
methamphetamine. The nature of the blue color was
unfortunately not determined but speculated to be an
additive dye. Attesting to the power of entertainment,
Mexican drug cartels are believed to be responsible for
these samples [19].

CONCLUSION

As should now be clear, Breaking Bad accurately portrays

methamphetamine synthesis. From pronunciation of
complex chemicals to the appearance of specific
reactions, they get it right—Bryan Cranston pronounces
chemical names better than some graduate students I
know. This is all possible because the staff at Breaking
Bad "do their homework," consulting experts like
associate chemistry professor Dr. Donna Nelson from
University of Oklahoma. No, they aren't perfect. Details
are sometimes overlooked, like condensers not being
connected to a water source and the order of synthesis
steps sometimes being wrong. The industrial scale
crystallization technique shown is unfamiliar to me, but
my synthesis experiences are on the relatively small
scale. While entertainment doesn't have to always get it
right, it is nice that it can. With the final episodes starting,
I hope that Breaking Bad continues to set a new standard
in narco-entertainment.
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Vinatoru, Mircea; Koenig, Max. Regenerative role of the
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